Addition compounds of cyclic diamines with vicinal glycols



ADDITION COMPOUNDS F CYCLIC DIAMlNES WITH VIClNAL GLYCOLS William W.Levis, Jr., Wyandotte, Mich., assignor to Wyandotte ChemicalsCorporation, Wyandotte, Mich., a corporation of Michigan No Drawing.Filed Dec. 23, 1957, Ser. No. 704,360

7 Claims. (Cl. 260-268) This invention relates to new compositions ofmatter comprising the addition compounds of vicinal glycols with cyclicdiamines. More particularly, this invention relates to additioncompounds formed by reacting a vicinal glycol of the formula:

. United States Patent() 2,969,365 Patented Jan. 24, 1961 employed, aswill be apparent from certain of the examples hereinafter set forth. Thecompositions of the invention are true addition compounds and, as such,there is no generally accepted theory whereby a structural formula canbe assigned to them. Although the temperature at which the reaction iscarried out is not critical, the addition compounds are, in general,prepared at or about room temperature.

Examples of vicina-l glycols which can be employed to prepare thecompositions of the invention include 1,2: propylene glycol, ethyleneglycol and 2,3-butylene glycol.

Although trimethylolethane is not a vicinal glycol, it does,

however, form a solid addition compound with the cyclic diamines.

Examples of the cyclic diamines which can be employed to prepare thecompositions of the invention include cis- 2,5-dimethylpiperazine,Z-methylpiperazine, piperazine, trans-2,5-dimethylpiperazine and2,3,5,6-tetramethylpiperazine.

The physical characteristics, including the melting points, of additioncompounds which are illustrative of the compounds of the invention areset forth in Table I below:

4 2,3,5,6-tetramethylpiperazine.

with a cyclic diamine of the formula:

H N R R .1 I. N H

wherein R is either a hydrogen, methyl or ethyl radical.

The compositions of the invention are either liquid or solid additioncompounds having well defined physical properties and can be readilyprepared by reacting a vicinal glycol with a cyclic diamine in asuitable container. The reaction can also be carried out in the presenceof a solvent or by melting the reactants together and adding arecrystallizing solvent to the melt.

The addition compounds of the invention are useful in the formation ofpolymers. Thus, mixed polyesterpolyamide polymers can be prepared byheating dibasic acids in the presence of the addition compounds of theinvention. Examples of the dibasic acids include adipic acid, maleicacid anhydride, terephthalic acid and sebacic acid. Also, the additioncompounds can be used as curing agents in the formation ofpolyurethanes. In addition-to the foregoing uses, certain of theaddition compounds such as the addition compound of piperazine and1,2-propylene glycol are useful as antihelminthics.

Since one mol of the vicinal glycol reacts with one mol of the cyclicdiamine to form the addition compounds of the invention, it ispreferable, therefore, to react the constituents of the additioncompounds on an equal mol basis. However, an excess of eitherconstituent can be The solid addition compounds can be prepared bydissolving the cyclic diamine in a suitable solvent such as benzene oracetone and adding the vicinal glycol thereto. The solution is heated inorder to completely solubilize the addition compound. Upon cooling thesolution, the addition compound recrystallizes from the solvent and canbe separated therefrom by filtration or decantation.

The liquid addition compounds can be prepared by dissolving the cyclicdiamine in a suitable solvent such as benzene or acetone and adding thevicinail glycol thereto. The resulting solution is heated and allowed tocool. The liquid addition compound can be recovered in good yield bydistilling 013? the solvent.

The following examples are given to illustrate this invention furtherand are not to be construed as limiting the invention except as definedin the appended claims.

Example I 10.0 grams of ethylene glycol were added to a flask containing22.84 grams of trans-2,5-DMP (DMP=dimethylp-iperazine) at an initialtemperature of 26 C. The temperature rose to 31 C. The contents of theflask were converted to a moist solid. The solid was dissolved inbenzene at a temperature of 50-55 C. and was recrystallized therefrom ata temperature of 10 C. There was obtained an addition compound ofethylene glycol and trans-2,5-DMP having a melting point of 84.0-84.5 C.and weighing 29.0 grams.

Example [I 11.42 grams of trans-2,5-DMP dissolved in 103 grams ofbenzene were added to 10 grams of ethylene glycol. A- turbid solutionresulted with the evolutionoi heat,

3 4 ,The solution was heated and it separated into two layers. solidaddition compound of trans-2,5-DMP and 1,2- The bottom layer wasethylene glycol. The top layer propylene glycol having a melting pointof 74.5-75.5 C. was decanted from the flask. Additional benzene wasExample XIII added to the ethylene glycol to remove the remainingaddition compound. The several benzene layers were 5 combined,concentrated, and allowed to cool. Upon cooling of the solution, therewas obtained 16.08 grams of an addition compound of ethylene glycol andtrans-2,5-

5.71 grams of trans-2,5-DMP were dissolved in 51 grams of benzene and4.51 grams of 2,3-butylene glycol were added thereto. The solution washeated and allowed to cool. A precipitate was separated from thesolution.

I y I c There was obtained a solid addition compound of trans- DMPhaving a melting point of 83.5 84.0 C. m ZSDMP and 2,3 buty1ene glycolhaving a melting Point Example of 101.s--102.s c. 2.50 grams of ethyleneglycol were added to 11.42 Example XIV grams of trans-2,5-DMP dissolvedin 103 grams of benzene. The solution was heated and allowed to cool.

grams of benzene and 4.51 grams of 2,3-butylene glycol There was nbamedan addition P ethylene were added thereto. After distilling oil? thebenzene, glycol 'D whlch had a meltmg Pomt of there was obtained a solidaddition compound of 2-meth- C'and welghed grams ylpiperazine and2,3-butylene glycol having a melting 5.01 grams of Z-methylpiperazinewere dissolved in 45 Examplev IV point of 7 677 C. 2.50 grams ofethylene glycol were added to 5.01 grams Examp XV of 2-methylpiperazinedissolved in 45 grams of benzene. 5,71 grams of ei -zj-DMP weredissolved in 50 ml. of A turbid emulsion resulted which was allowed tosettle. benzene d 4 51 grams f 2,3-buty1' ly ol we e added The benzenewas remov d therefr m- Th r was thereto. The solution was heated andallowed to cool. tainfid a fl flfiditicm COIIIPmmd of Ethylene glycoland There was obtained a solid addition compound of cis-2-methylp1perazme- 2,5-DMP and 2,3-butylene glycol having a meltingpoint Example. V of 66-67 C. 4.31 grams of piperazine were reacted with3.10- grams ExamP XVI of ethylene glycol in the presence of 50 ml. ofbenzene. 431 grams f piperazine were di olved in 50 m1, of The Soluti ns heated and allowed @001 The P benzene and 4.51 grams of 2,3-butyleneglycol were added cipitateobtainedwas. recrystallized from benzene.There th Th l ti was he ted d allowed to cool. was obtained an additioncompound Of ethylene glycol There was obtained a solid addition cgmpoundof piper. and Piperazine having a melting. Point of azine and2,3-butylene glycol having a melting point of Example VI '99.0-99.5 C.5.71 grams of cis-2,5-DMP were reacted with 3.1 grams Example XVII ofethylene glycol in the presence of 50 ml. of benzene. 2,3 butyleneglycol was reacted with 2,3,5,6-tetrameth- After distilling off thebenzene, there was obtained a liquid ylpiperazine. Ther Was o tained aSolid addition oomaddition compound of ethylene glycol and cis-2,5-DMP.pound. Three isomers of the solid addition compound Example VII wereisolated and had melting points of l42.5-143.0 C.,2,3,5,6-tetramethylpiperazinewas reacted with ethylene 109'0409'7 and71-72 glycol. There was obtained a solid addition compound Example XVIIIof tetramethylpiperazine and ethylene glycol having a 5 grams oftrimethylolethane were added to 28 grams melt1ngpo1ntofll 6125 C. oftrans-2,5-DMP and heat was applied until a melt Example VIII formed.Upon cooling, but before complete solidifica- 431 grams of piperazinewere reacted with 33 grams tron, benzene was added; The resulting80111121011. was

of 12 pmpy1ene glycol in the presence of benzemfl The heated and allowedto cool. There was obtained a solid solution was heated and allowed tocool. A solid product addmon f of methylolethaneo and precipitated fromthe solution and was recrystallized from. DMP havmg melting Pomt ofbenzene. There was obtained a solid addition compound what a 1S: ofpipemzine and 1,2 propy1ene glycol having a mam-mg 1 An add1t1oncompound ln-accordance with the folpoint. of 20 25o lowing formula:

Example IX 7 R g g 1 5.71 grams of cis-2,5-DMP were reacted with 3.80 n-(1 -0H R R grams of propylene glycol in the presence of 50 of benzene.After distilling. 01f the benzene, there was ob- R N R tained at liquidaddition compound of cis-2,5-DMP and R H L -P PY glycol whereinR-amember selected from the group consisting ple X of "H,.metl1yl andethylradicals. 1,2-propylene glycol was reacted with 2,3,-5,6-tetra- 2.An-add-ition compound according to the formula: methylpiperazine. Therewas obtained a solid addition H- cornpound of, 1,2-propylene glycol andtetramethylpiper- & azine. A

Example XI H -OH C a CH: 5.01 grams of 2-methylpiperazine were dissolvedin 45 OH-' CH1 H grams of benzene and 3.80 grams of 1,2-propylene glycolN were added thereto. After distilling oif the benzene, there A wasobtained 7.8 grams of a liquid addition compound of Z-methylpiperazineand 1,2-propyleneglycol. H Example XII H 1.

5 .71 grams of trans-2,5-DMP Were dissolved in 5.1 H-( J0H grams ofbenzene and 3.80 grams of 1,2-propylene glycol 11 ---OH'.Z CH2 wereadded thereto. The solutionwas heated and allowed to 0001. A precipitatewas separated from the solution andrecrystallized from benzene. Therewas obtained a- E 4. An addition compound according to the formula:

5. An addition compound according to the formula:

11-c-0H' (ma-e41 H-COH:

I H l 6. An addition compound according to the formula:

7. A process which comprises bringing into contact at about roomtemperature a compound selected from the group consisting of glycols ofthe formula:

OH o1: R-c-c-R and trimethylolethane with a cyclic diamine of theformula:

N R R wherein R is a member selected from the group consisting ofhydrogen, methyl and ethyl radicals and isolating an addition product.

References Cited in the file of this patent UNITED STATES PATENTSSchreyer July 10, 1956 Hadler et al Oct. 22, 1957 OTHER REFERENCES

1. AN ADDITION COMPOUND IN ACCORDANCE WITH THE FOLLOWING FORMULA: